Crystal structure and microwave dielectric properties of Ca[(Li1/3Nb2/3) 0.92Zr0.08]O3−δ−xTiO2(0≤x≤0.2) ceramics were investigated. A single phase with orthorhombic perovskite structure was obtained at x=0.0~0.1. With an increasing of Ti4+ content, the Qf value decreased due to a decrease of the degree of B-site 1:2 ordering. However, the τf value firstly increased from-14.2ppm /°C to -6.6ppm/°C, and then moved to the negative direction. When x=0.05, the optimum microwave dielectric properties: εr=32.8, Qf =19460GHz and τf =−8.3 ppm/°C.